CN113429783A - Low-friction low-abrasion high-temperature nylon and preparation method thereof - Google Patents

Low-friction low-abrasion high-temperature nylon and preparation method thereof Download PDF

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CN113429783A
CN113429783A CN202110777113.2A CN202110777113A CN113429783A CN 113429783 A CN113429783 A CN 113429783A CN 202110777113 A CN202110777113 A CN 202110777113A CN 113429783 A CN113429783 A CN 113429783A
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low
modified
nylon
friction
temperature nylon
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许龙
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Zhejiang Punetu New Material Technology Co ltd
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Zhejiang Punetu New Material Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
    • C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2409/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08J2409/02—Copolymers with acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2481/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
    • C08J2481/02—Polythioethers; Polythioether-ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
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    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds

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Abstract

The invention relates to C08L77/00, in particular to low-friction low-abrasion high-temperature nylon and a preparation method thereof. The high-temperature nylon is prepared from the following raw materials in parts by weight: 100 parts of semi-aromatic nylon, 30-60 parts of reinforcing material and 2-10 parts of inorganic filler. By adding the glass fiber and the polyphenylene sulfide with proper dosage, especially the modified glass fiber of the amino silane coupling agent, and the combined action of the polyphenylene sulfide and the semi-aromatic nylon, the high temperature resistance and the surface hardness can be obviously improved and the abrasion can be reduced by utilizing the dispersion and the cross-linking network of the glass fiber. By adding the reinforcing filler, such as fluorine-containing silane coupling agent modified montmorillonite, the flowability brought by the addition of glass fibers and the formation of a cross-linked network can be reduced greatly, the flowability and the processing stability are improved, the friction coefficient is reduced, and the wear resistance is further reduced.

Description

Low-friction low-abrasion high-temperature nylon and preparation method thereof
Technical Field
The invention relates to C08L77/00, in particular to low-friction low-abrasion high-temperature nylon and a preparation method thereof.
Background
Nylon is a thermoplastic resin including a repeating amide bond, and can be classified into aliphatic, aromatic and semi-aromatic nylon according to whether the nylon contains an aromatic ring, wherein the semi-aromatic nylon is a new type of nylon material, and can be used in a plurality of fields such as automobiles, medical instruments, photoelectricity and the like.
CN112226072A discloses a semi-aromatic nylon modified material and a preparation method thereof, wherein the raw materials comprise semi-aromatic nylon, glass fiber, a flame retardant, an antioxidant, a lubricant and an acid-absorbing agent, and the semi-aromatic nylon modified material can prevent semi-aromatic nylon products from corroding equipment in the modification process and prolong the service life of the equipment for production, injection molding and the like.
However, the existing semi-aromatic nylon material has the problems of poor wear resistance, high friction coefficient and high friction loss, and the prepared nylon is difficult to meet the requirement of higher temperature.
Disclosure of Invention
In order to solve the above problems, the first aspect of the present invention provides a low-friction low-abrasion high-temperature nylon, which is prepared from the following raw materials in parts by weight: 100 parts of semi-aromatic nylon, 30-60 parts of reinforcing material and 2-10 parts of inorganic filler.
In a preferred embodiment of the present invention, the semi-aromatic nylon is prepared from an aromatic dibasic acid and an aliphatic diamine, the aromatic dibasic acid is terephthalic acid and/or isophthalic acid, and the aromatic diamine is one or more selected from butanediamine, pentanediamine, hexanediamine, heptanediamine, and octanediamine.
As a preferable technical solution of the present invention, the reinforcing material includes inorganic reinforcing fibers, and the inorganic reinforcing fibers include at least one of glass fibers, carbon fibers, aramid fibers, and basalt fibers.
As a preferred technical solution of the present invention, the reinforcing material further includes an organic reinforcing material, and the organic reinforcing material includes one or more of polyphenylene sulfide, polyester, and polyurethane.
As a preferable technical scheme of the invention, the inorganic reinforced fiber is a modified inorganic reinforced fiber, and the preparation raw materials of the modified reinforced fiber comprise an aminosilane coupling agent and the inorganic reinforced fiber in a weight ratio of (2-5): 100.
as a preferable technical scheme of the invention, the organic reinforcing material is a modified organic reinforcing material, and the preparation raw materials of the modified organic reinforcing material comprise inorganic particles and an organic reinforcing material in a weight ratio of (3-5): 100.
in a preferred embodiment of the present invention, the inorganic particles are selected from one or more of calcium carbonate, zinc oxide, magnesium oxide, and graphite.
In a preferred embodiment of the present invention, the inorganic filler is selected from one or more of montmorillonite, silicate, carbon black, graphite, and diatomaceous earth.
As a preferable technical scheme of the invention, the inorganic filler is a modified inorganic filler, and the preparation raw materials of the modified inorganic filler comprise a fluorine-containing silane coupling agent and the inorganic filler in a weight ratio of (1-3): 100.
the second aspect of the invention provides a preparation method of the low-friction low-abrasion high-temperature nylon, which comprises the following steps: and blending and extruding the preparation raw materials of the high-temperature nylon to obtain the high-temperature nylon.
Compared with the prior art, the invention has the following beneficial effects:
(1) the glass fiber and the polyphenylene sulfide, especially the aminosilane coupling agent modified glass fiber, are added with proper dosage, and the glass fiber and the polyphenylene sulfide and the semi-aromatic nylon are acted together, and the dispersion and the cross-linking network of the glass fiber are utilized, so that the high temperature resistance and the surface hardness can be obviously improved, and the abrasion is reduced;
(2) by adding the reinforcing filler, such as fluorine-containing silane coupling agent modified montmorillonite, the flowability brought by the addition of glass fibers and the formation of a cross-linked network can be reduced greatly, the flowability and the processing stability are improved, the friction coefficient is reduced, and the wear resistance is further reduced.
(3) By adding the nitrile rubber, such as high-molecular nitrile rubber and solid nitrile rubber, the nitrile rubber and semi-aromatic nylon can act together under the condition of less addition amount, so that the abrasion resistance reduction caused by adding the fluorine-containing silane, the lubricant and the like is avoided, and the nylon material with low friction, abrasion and high abrasion resistance is obtained.
Detailed Description
As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items. Expressions such as "at least one (of … …)" when preceding or succeeding a list of elements modify the entire list of elements without modifying individual elements of the list.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the inventive concept. The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. Hereinafter, it will be understood that terms such as "comprising," "having," "including," and "containing" used herein are intended to mean that there are features, numbers, steps, actions, components (parts), portions, and/or combinations thereof disclosed in the specification, and are not intended to preclude the possibility that one or more additional features, numbers, steps, actions, components (parts), portions, and/or combinations thereof may be present or may be added. The term "or" means "and/or". The expression "/" can be interpreted as "and" or "depending on the context.
Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this general inventive concept belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the present disclosure and the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
The present invention is illustrated by the following specific embodiments, but is not limited to the specific examples given below.
The invention provides a low-friction low-abrasion high-temperature nylon, which is prepared from the following raw materials in parts by weight: 100 parts of semi-aromatic nylon, 30-60 parts of reinforcing material and 2-10 parts of inorganic filler.
Semi-aromatic nylon
In one embodiment, the semi-aromatic nylon of the present invention is prepared from an aromatic dibasic acid and an aliphatic diamine, wherein the aromatic dibasic acid is terephthalic acid and/or isophthalic acid, and the aromatic diamine is selected from one or more of butanediamine, pentanediamine, hexanediamine, heptanediamine and octanediamine. Examples of semi-aromatic nylons include, but are not limited to, nylon 4T, nylon 6T, nylon 9T, nylon 10T, nylon 11T, nylon 12T. The semi-aromatic nylon of the present invention may be self-made and purchased, without specific limitation, and when purchased, may be purchased from mitsui chemical, dupont, etc., such as nylon 6TFR52G45NHF, nylon 6T HTN53G50LRHF NC010, nylon 6T HTN53G50LRHF WT619A, nylon 6T HTNFE18502 YL531A of dupont.
Reinforcing material
In one embodiment, the reinforcement material of the present invention comprises inorganic reinforcing fibers comprising at least one of glass fibers, carbon fibers, aramid fibers, basalt fibers.
Preferably, the reinforcing material of the present invention further comprises an organic reinforcing material, and the organic reinforcing material comprises one or more of polyphenylene sulfide, polyester and polyurethane.
More preferably, the weight ratio of the inorganic reinforcing fibers and the organic reinforcing material of the present invention is 1: (0.2-0.4).
Further preferably, the inorganic reinforced fiber is a modified inorganic reinforced fiber, and the modified reinforced fiber is prepared from the following raw materials in parts by weight (2-5): 100.
still more preferably, the aminosilane coupling agent according to the present invention is one or more selected from the group consisting of N- (β -aminoethyl) - γ -aminopropyltrimethoxysilane, γ -aminopropyltriisooxysilane, γ -aminopropyltrimethoxysilane, γ -aminopropyltriethoxysilane, N- (β -aminoethyl) - γ -aminopropylmethyldiethoxysilane, γ -aminopropylmethyldimethoxysilane, and γ -aminopropylethoxydimethylsilane, without being particularly limited.
The modified inorganic reinforcing fiber of the present invention is prepared according to a method well known in the art, and is not particularly limited, and in one embodiment, the modified reinforcing fiber is prepared by a method comprising: drying the inorganic reinforced fiber at 300-600 ℃ for 0.5-1 h, adding the inorganic reinforced fiber into an aminosilane coupling agent aqueous solution, reacting at 50-60 ℃ for 3-5 h, washing and drying to obtain the reinforced fiber.
In a preferred embodiment, the glass fiber of the present invention has a filament diameter of 6 to 10 μm and a length of 3 to 4.5mm, such as ECS series glass fibers of Chongqing International composite materials, Inc., for example, 301CL, 301HP, 3014B, 301X 1. The diameters of the monofilaments 301CL, 301HP, 3014B and 301X1 are 6-10 μm, and the length of the glass fiber is 3-4.5 mm.
The inventor finds that a material with higher strength is obtained by using semi-aromatic nylon and a reinforcing material, such as glass fiber and the like, but the inventor finds that the effect of reinforcing glass fiber and the like is difficult to exert because the compatibility of the reinforcing material, such as glass fiber and the like, and nylon is poor, and the inventor finds that the glass fiber modified by using an aminosilane coupling agent utilizes the aminosilane coupling agent as a bridge, on one hand, the siloxane structure in the aminosilane coupling agent is connected with the glass fiber, on the other hand, the amide structure of amino and nylon and residual carboxyl are subjected to physical and chemical crosslinking, the mutual dispersion and compatibility of the glass fiber and nylon can be promoted, and the inventor unexpectedly finds that the high-temperature resistance is favorably improved while the strength is promoted.
In a more preferred embodiment, the organic reinforcing material of the present invention is a modified organic reinforcing material, and the modified organic reinforcing material is prepared from inorganic particles and an organic reinforcing material, wherein the weight ratio of the inorganic particles to the organic reinforcing material is (3-5): 100.
in a further preferred embodiment, the inorganic particles according to the present invention are selected from one or more of calcium carbonate, zinc oxide, magnesium oxide, graphite. Calcium carbonate is preferred. The calcium carbonate is stearic acid modified calcium carbonate, and can be prepared or purchased by self, such as from Guangdong source epitaxy powder calcium carbonate factories.
In a further preferred embodiment, the mesh number of the inorganic particles of the present invention is 8000 to 12500 mesh.
In addition, the inventor finds that the abrasion resistance can be reduced while the strength is increased along with the increase of the glass fiber, and the inventor surprisingly finds that when nonpolar and high-strength polyphenylene sulfide is used, particularly inorganic particles with a certain particle size, such as calcium carbonate and the like, are attached to the surface of the polyphenylene sulfide, the increase of the abrasion resistance can be further promoted while the high temperature resistance and the strength of the nylon material are improved, which is probably because calcium carbonate is secondarily agglomerated by using the polyphenylene sulfide modified by more calcium carbonate, the dispersion among the polyphenylene sulfides is promoted, and simultaneously the calcium carbonate can also be acted with amino groups on the glass fiber, so that the calcium carbonate with a certain particle size is indirectly attached to the glass fiber, and the surface hardness is improved due to the interaction winding of the glass fiber-polyphenylene sulfide-semi-aromatic nylon when the glass fiber is rubbed, particularly high-temperature rubbing, so that the abrasion is a loss of glass fiber or nonpolar polyphenylene sulfide.
The inventor finds that when calcium carbonate with larger particle size is used for modification or the dosage of the calcium carbonate is lower, the dispersion among polyphenylene sulfide is not facilitated, so that the dispersion of glass fibers is driven, the action of the calcium carbonate with the surface amino groups of the glass fibers is increased, the surface hardness of the material is influenced, and the abrasion resistance and the strength are reduced.
The modified organic reinforcing material of the present invention is prepared according to a method well known in the art, and is not particularly limited, and in one embodiment, the method for preparing the modified organic reinforcing material comprises: and melting and extruding the inorganic particles and the organic reinforcing material at 200-400 ℃, and crushing to obtain the modified organic reinforcing material.
In a further preferred embodiment, the modified organic reinforcing material of the present invention has an average particle size of 300 to 600 μm.
Inorganic filler
In one embodiment, the inorganic filler of the present invention is selected from one or more of montmorillonite, silicate, carbon black, graphite, diatomaceous earth, preferably montmorillonite.
Preferably, the inorganic filler is a modified inorganic filler, and the preparation raw materials of the modified inorganic filler comprise a fluorine-containing silane coupling agent and the inorganic filler in a weight ratio of (1-3): 100.
the modified inorganic filler of the present invention is prepared according to a method well known in the art, and is not particularly limited, and in one embodiment, the modified inorganic filler is prepared by a method comprising: adding an inorganic filler into an aqueous solution containing a fluorine-containing silane coupling agent, reacting for 2-4 h at 70-80 ℃, washing, and drying to obtain the modified inorganic filler.
More preferably, the fluorine-containing silane coupling agent of the present invention is selected from one or more of trifluoropropylmethyldiethoxysilane, trifluoropropylmethyldimethoxysilane, tridecafluorooctyltrimethoxysilane, trifluoropropyltriethoxysilane, trifluoropropyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane, tridecafluorooctyltriethoxysilane, preferably trifluoropropylmethyldiethoxysilane, trifluoropropylmethyldimethoxysilane, trifluoropropyltriethoxysilane, trifluoropropyltrimethoxysilane.
The inventor finds that semi-aromatic nylon has poor fluidity due to the existence of an aromatic structure, the fluidity is further reduced along with the use of a reinforcing material, and the processing stability is influenced, while the current lubricants, such as small molecular lubricants and the like, have influence on the strength and the high-temperature performance, and the inventor finds that the fluidity is promoted, and simultaneously, the strength, the toughness and the surface smoothness of the prepared material are improved, and the occurrence of floating fibers is reduced by using the modified inorganic filler, particularly the diatomite modified by the fluorine-containing silane coupling agent.
The reason is probably that hydrogen bonds can be formed by using the diatomite modified by the fluorine-containing silane coupling agent, and then the diatomite is contacted with the aryl amide group of the nylon and the amino coupling agent group of the glass fiber, and simultaneously, the slip and the dissociation of the lamellar diatomite are promoted in the process of blending and extruding, so that the diatomite with the fluorine-containing silane grafting structure in submicron or even nanometer size is dispersed between the glass fiber and the semi-aromatic nylon, the improvement of the fluidity is promoted, the processing performance is improved, the blending of the raw materials is promoted, the high-strength, high-toughness and smooth-surfaced materials are obtained, the friction coefficient is reduced, and the wear resistance is further reduced.
The inventor finds that the length of the fluorine-containing silane coupling agent needs to be controlled, and when the fluorine-containing chain is longer, the further improvement of the fluidity and the wear resistance is not facilitated, probably because the longer fluorine-containing chain is difficult to enter between lamellar structures of the montmorillonite, the dissociation and the dispersion of the montmorillonite are influenced, the fluidity is reduced, the appearance of the prepared material is rougher, and the improvement of the wear resistance is influenced.
In one embodiment, the raw materials for preparing the high-temperature nylon comprise 2-5 parts by weight of a lubricant.
Lubricant agent
In one embodiment, the lubricant of the present invention is selected from one or more of stearyl alcohol, silicone, ethylene bis stearamide, and ethylene homopolymeric wax, and is not particularly limited.
In one embodiment, the high-temperature nylon provided by the invention comprises 2-10 parts by weight of plasticizer.
Plasticizer
In one embodiment, the plasticizer of the present invention is selected from one or more of polyethylene glycol, epoxidized soybean oil, liquid paraffin, solid nitrile rubber (NBR), liquid nitrile rubber (LNBR).
The invention is not specifically limited to manufacturers of solid nitrile rubber and liquid nitrile rubber, and examples of nitrile rubber include NBR1704 (mass percent of acrylonitrile: 17-20 wt%), NBR2707 (mass percent of acrylonitrile: 27-30 wt%), NBR3604 (mass percent of acrylonitrile: 36-40 wt%), NBR3606 (mass percent of acrylonitrile: 36-40 wt%), N230S (mass percent of acrylonitrile: 33.5-36.5 wt%), and N240S (mass percent of acrylonitrile: 24.5-27.5 wt%), which meet GB5577-85 standards.
As examples of the liquid nitrile rubber, mention may be made of GREENBABY LR brand LR-899 (acrylonitrile mass percent of 18-20 wt%), LR-899-13 (acrylonitrile mass percent of 28-33 wt%), LR-892 (acrylonitrile mass percent of 28-33 wt%), LR-894 (acrylonitrile mass percent of 38-40 wt%), LR-LNBR820N (acrylonitrile mass percent of 26-30 wt%), LR-LNBR820 (acrylonitrile mass percent of 28-33 wt%), LR-820-3M (acrylonitrile mass percent of 28-33 wt%), LR-810 (acrylonitrile mass percent of 18-20 wt%), and the like, LR-815M (acrylonitrile mass percent of 28-30 wt%) and LR-815MM (acrylonitrile mass percent of 28-30 wt%).
Preferably, the weight ratio of the solid nitrile rubber to the liquid nitrile rubber is (1-2): (1-2).
More preferably, the mass percent of acrylonitrile in the solid nitrile rubber is 22-35 wt%, and the mass percent of acrylonitrile in the liquid nitrile rubber is 22-35 wt%.
In addition, the inventor finds that the fluorine-containing modified inorganic filler promotes the increase of the fluidity and also partially moves to the surface of the material along with the melt blending, so that part of glass fibers are exposed on the surface, and the problem of fiber floating is difficult to completely eliminate.
The reason for this is probably that the high-polarity nitrile rubber is added, the dispersion is promoted by utilizing the good lubricity of the liquid nitrile rubber with lower molecular weight, meanwhile, the intermolecular force and winding are generated between the solid nitrile rubber with higher molecular weight and the polyamide and the glass fiber, so that the diatomite modified by the fluorine coupling agent and the glass fiber are competitively adsorbed, and the macromolecular chain of the solid rubber obstructs the movement of the glass fiber and the like to the surface of the material, so that the adhesive force between the glass fiber and the like and the polyamide and the nitrile rubber and the like is increased, thereby avoiding the problems of fiber floating and the like.
In addition, the inventor finds that the content of the butyronitrile in the nitrile rubber needs to be controlled not to be too high, and when the content is too high, the acting force with other preparation raw materials is too large, but the improvement of the fluidity and the blending of the raw materials are not facilitated, so that the improvement of the wear resistance, the strength and the like are influenced.
The second aspect of the present invention provides a method for preparing the high temperature nylon, which comprises: and blending and extruding the preparation raw materials of the high-temperature nylon to obtain the high-temperature nylon. The inventors have found that by using semi-aromatic nylon and fibers modified with a suitable coupling agent as a continuous phase and a dispersed phase and dispersing polyphenylene sulfide, an inorganic filler, nitrile rubber, etc. at the interface thereof, the resulting material has a high cross-over and coating structure, thereby reducing friction and abrasion when subjected to friction, avoiding friction loss, particularly friction loss at high temperature and high humidity, and improving high temperature resistance and strength of the material.
Examples
Example 1
The embodiment provides a low-friction low-abrasion high-temperature nylon, which is prepared from the following raw materials in parts by weight: 100 parts of semi-aromatic nylon, 50 parts of reinforcing material, 8 parts of inorganic filler, 3 parts of lubricant and 6 parts of plasticizer, wherein the semi-aromatic nylon is nylon 6T HTN53G50LRHF NC010, the reinforcing material comprises inorganic reinforcing fibers and organic reinforcing material, and the weight ratio is 1: 0.3, the inorganic reinforced fiber is modified inorganic reinforced fiber, the preparation raw material of the modified reinforced fiber comprises amino silane coupling agent and glass fiber, the weight ratio is 4: 100, the aminosilane coupling agent is N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, and the preparation method of the modified reinforcing fiber comprises the following steps: drying glass fibers at 400 ℃ for 0.5h, adding an aminosilane coupling agent aqueous solution, reacting at 55 ℃ for 4h, washing, and drying to obtain the reinforced fibers, wherein the glass fibers are 301CL, the organic reinforced material is a modified organic reinforced material, and the preparation raw materials of the modified organic reinforced material comprise inorganic particles and polyphenylene sulfide in a weight ratio of 4: 100, the inorganic particles are stearic acid modified calcium carbonate, the mesh number is 10000 meshes, and the preparation method of the modified organic reinforced material comprises the following steps: melting and extruding inorganic particles and polyphenylene sulfide at 300 ℃, and crushing to obtain the organic reinforced material, wherein the average particle size of the modified organic reinforced material is 500 mu m, the inorganic filler is a modified inorganic filler, and the preparation raw materials of the modified inorganic filler comprise fluorine-containing silane coupling agent and montmorillonite in a weight ratio of 2: 100, the fluorine-containing silane coupling agent is trifluoropropylmethyldiethoxysilane, and the preparation method of the modified inorganic filler comprises the following steps: adding an inorganic filler into an aqueous solution of a fluorine-containing silane coupling agent, reacting for 3 hours at 75 ℃, washing and drying to obtain the modified inorganic filler, wherein the lubricant is ethylene homopolymerized wax, and the plasticizer is polyethylene glycol-4000.
The embodiment also provides a preparation method of the high-temperature nylon, which comprises the following steps: and blending and extruding the preparation raw materials of the high-temperature nylon to obtain the high-temperature nylon.
Example 2
The embodiment provides a low-friction low-abrasion high-temperature nylon, which is prepared from the following raw materials in parts by weight: 100 parts of semi-aromatic nylon, 50 parts of reinforcing material, 8 parts of inorganic filler, 3 parts of lubricant and 6 parts of plasticizer, wherein the semi-aromatic nylon is nylon 6T HTN53G50LRHF NC010, the reinforcing material comprises inorganic reinforcing fibers and organic reinforcing material, and the weight ratio is 1: 0.3, the inorganic reinforced fiber is modified inorganic reinforced fiber, the preparation raw material of the modified reinforced fiber comprises amino silane coupling agent and glass fiber, the weight ratio is 4: 100, the aminosilane coupling agent is N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, and the preparation method of the modified reinforcing fiber comprises the following steps: drying glass fibers at 400 ℃ for 0.5h, adding an aminosilane coupling agent aqueous solution, reacting at 55 ℃ for 4h, washing, and drying to obtain the reinforced fibers, wherein the glass fibers are 301CL, the organic reinforced material is a modified organic reinforced material, and the preparation raw materials of the modified organic reinforced material comprise inorganic particles and polyphenylene sulfide in a weight ratio of 4: 100, the inorganic particles are stearic acid modified calcium carbonate, the mesh number is 10000 meshes, and the preparation method of the modified organic reinforced material comprises the following steps: melting and extruding inorganic particles and polyphenylene sulfide at 300 ℃, and crushing to obtain the organic reinforced material, wherein the average particle size of the modified organic reinforced material is 500 mu m, the inorganic filler is a modified inorganic filler, and the preparation raw materials of the modified inorganic filler comprise fluorine-containing silane coupling agent and montmorillonite in a weight ratio of 2: 100, the fluorine-containing silane coupling agent is trifluoropropylmethyldiethoxysilane, and the preparation method of the modified inorganic filler comprises the following steps: adding an inorganic filler into an aqueous solution of a fluorine-containing silane coupling agent, reacting for 3 hours at 75 ℃, washing and drying to obtain the modified inorganic filler, wherein the lubricant is ethylene homopolymerized wax, and the plasticizer is solid nitrile butadiene rubber NBR2707 and liquid nitrile butadiene rubber LR-892 in a weight ratio of 1: 1.
the embodiment also provides a preparation method of the high-temperature nylon, which comprises the following steps: and blending and extruding the preparation raw materials of the high-temperature nylon to obtain the high-temperature nylon.
Example 3
The embodiment provides a low-friction low-abrasion high-temperature nylon, which is prepared from the following raw materials in parts by weight: 100 parts of semi-aromatic nylon, 60 parts of reinforcing material, 10 parts of inorganic filler, 5 parts of lubricant and 10 parts of plasticizer, wherein the semi-aromatic nylon is nylon 6T HTN53G50LRHF NC010, the reinforcing material comprises inorganic reinforcing fiber and organic reinforcing material, and the weight ratio is 1: 0.4, the inorganic reinforced fiber is modified inorganic reinforced fiber, the preparation raw material of the modified reinforced fiber comprises amino silane coupling agent and glass fiber, and the weight ratio is 5: 100, the aminosilane coupling agent is gamma-aminopropyltrimethoxysilane, and the preparation method of the modified reinforcing fiber comprises the following steps: drying glass fibers at 400 ℃ for 0.5h, adding an aminosilane coupling agent aqueous solution, reacting at 55 ℃ for 4h, washing, and drying to obtain the reinforced fibers, wherein the glass fibers are 301HP, the organic reinforced material is a modified organic reinforced material, and the modified organic reinforced material is prepared from the following raw materials in a weight ratio of 5: 100, the inorganic particles are stearic acid modified calcium carbonate, the mesh number is 12500 meshes, and the preparation method of the modified organic reinforcing material comprises the following steps: melting and extruding inorganic particles and polyphenylene sulfide at 300 ℃, and crushing to obtain the organic reinforced material, wherein the average particle size of the modified organic reinforced material is 600 mu m, the inorganic filler is a modified inorganic filler, and the preparation raw materials of the modified inorganic filler comprise fluorine-containing silane coupling agent and montmorillonite in a weight ratio of 3: 100, the fluorine-containing silane coupling agent is trifluoropropylmethyldimethoxysilane, and the preparation method of the modified inorganic filler comprises the following steps: adding an inorganic filler into an aqueous solution of a fluorine-containing silane coupling agent, reacting for 3 hours at 75 ℃, washing and drying to obtain the modified inorganic filler, wherein the lubricant is ethylene homopolymerized wax, the plasticizer is solid nitrile rubber N240S and liquid nitrile rubber LR-LNBR820N, and the weight ratio is 2: 1.
the embodiment also provides a preparation method of the high-temperature nylon, which comprises the following steps: and blending and extruding the preparation raw materials of the high-temperature nylon to obtain the high-temperature nylon.
Example 4
The embodiment provides a low-friction low-abrasion high-temperature nylon, which is prepared from the following raw materials in parts by weight: 100 parts of semi-aromatic nylon, 40 parts of reinforcing material, 4 parts of inorganic filler, 2 parts of lubricant and 4 parts of plasticizer, wherein the semi-aromatic nylon is nylon 6T HTN53G50LRHF NC010, the reinforcing material comprises inorganic reinforcing fiber and organic reinforcing material, and the weight ratio is 1: 0.2, the inorganic reinforced fiber is modified inorganic reinforced fiber, the preparation raw material of the modified reinforced fiber comprises amino silane coupling agent and glass fiber, the weight ratio is 2: 100, the amino silane coupling agent is gamma-aminopropyl ethoxy dimethylsilane, and the preparation method of the modified reinforcing fiber comprises the following steps: drying glass fibers at 400 ℃ for 0.5h, adding an aminosilane coupling agent aqueous solution, reacting at 55 ℃ for 4h, washing, and drying to obtain the reinforced fibers, wherein the glass fibers are 3014B, the organic reinforced material is a modified organic reinforced material, and the preparation raw materials of the modified organic reinforced material comprise inorganic particles and polyphenylene sulfide in a weight ratio of 3: 100, the inorganic particles are stearic acid modified calcium carbonate, the mesh number is 8000 meshes, and the preparation method of the modified organic reinforcing material comprises the following steps: melting and extruding inorganic particles and polyphenylene sulfide at 300 ℃, and crushing to obtain the organic reinforced material, wherein the average particle size of the modified organic reinforced material is 300 mu m, the inorganic filler is a modified inorganic filler, and the preparation raw materials of the modified inorganic filler comprise fluorine-containing silane coupling agent and montmorillonite in a weight ratio of 1: 100, the fluorine-containing silane coupling agent is trifluoropropyltrimethoxysilane, and the preparation method of the modified inorganic filler comprises the following steps: adding an inorganic filler into an aqueous solution of a fluorine-containing silane coupling agent, reacting for 3 hours at 75 ℃, washing and drying to obtain the modified inorganic filler, wherein the lubricant is ethylene homopolymerized wax, and the plasticizer is solid nitrile butadiene rubber NBR2707 and liquid nitrile butadiene rubber LR-820, and the weight ratio is 1: 2.
the embodiment also provides a preparation method of the high-temperature nylon, which comprises the following steps: and blending and extruding the preparation raw materials of the high-temperature nylon to obtain the high-temperature nylon.
Example 5
The embodiment provides a low-friction low-abrasion high-temperature nylon, which is prepared from the following raw materials in parts by weight: 100 parts of semi-aromatic nylon, 50 parts of reinforcing material, 8 parts of inorganic filler, 3 parts of lubricant and 6 parts of plasticizer, wherein the semi-aromatic nylon is nylon 6T HTN53G50LRHF NC010, the reinforcing material comprises inorganic reinforcing fibers and organic reinforcing material, and the weight ratio is 1: 0.3, the inorganic reinforced fiber is modified inorganic reinforced fiber, the preparation raw material of the modified reinforced fiber comprises amino silane coupling agent and glass fiber, the weight ratio is 4: 100, the aminosilane coupling agent is N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, and the preparation method of the modified reinforcing fiber comprises the following steps: drying glass fibers at 400 ℃ for 0.5h, adding an aminosilane coupling agent aqueous solution, reacting at 55 ℃ for 4h, washing, and drying to obtain the reinforced fibers, wherein the glass fibers are 301CL, the organic reinforced material is a modified organic reinforced material, and the preparation raw materials of the modified organic reinforced material comprise inorganic particles and polyphenylene sulfide in a weight ratio of 0.5: 100, the inorganic particles are stearic acid modified calcium carbonate, the mesh number is 10000 meshes, and the preparation method of the modified organic reinforced material comprises the following steps: melting and extruding inorganic particles and polyphenylene sulfide at 300 ℃, and crushing to obtain the organic reinforced material, wherein the average particle size of the modified organic reinforced material is 500 mu m, the inorganic filler is a modified inorganic filler, and the preparation raw materials of the modified inorganic filler comprise fluorine-containing silane coupling agent and montmorillonite in a weight ratio of 2: 100, the fluorine-containing silane coupling agent is trifluoropropylmethyldiethoxysilane, and the preparation method of the modified inorganic filler comprises the following steps: adding an inorganic filler into an aqueous solution of a fluorine-containing silane coupling agent, reacting for 3 hours at 75 ℃, washing and drying to obtain the modified inorganic filler, wherein the lubricant is ethylene homopolymerized wax, and the plasticizer is solid nitrile butadiene rubber NBR2707 and liquid nitrile butadiene rubber LR-892 in a weight ratio of 1: 1.
the embodiment also provides a preparation method of the high-temperature nylon, which comprises the following steps: and blending and extruding the preparation raw materials of the high-temperature nylon to obtain the high-temperature nylon.
Evaluation of Performance
1. Mechanical properties: mechanical property tests are carried out on the high-temperature nylon provided in examples 1-3, and the results show that the tensile strength (GB/T1040.2, +23 ℃, 2mm/min) is more than 150000MPa, the bending strength (GB/T9341, +23 ℃, 2mm/min) is more than 250MPa, and the notched Izod impact strength (GB/T1843, +23 ℃, 2.75J hammer) is more than 16KJ/m2The heat distortion temperature (GB/T1634.2, 1.82MPa) is more than 280 ℃.
2. Wear resistance: the abrasion resistance (1000g, 1000r) of the high temperature nylon provided in the test examples according to GB/T5478-.
3. Fluidity: the melt indices at 360 ℃/2.16Kg, R and D respectively, of the high temperature nylon provided in the examples and pure PA6T calculated according to GB/T36820 were calculated to be (R-D)/D x 100%, wherein the growth rate is superior at greater than 300%, the growth rate is 300% or less, good at greater than 250%, the growth rate is 250% or less, and medium at greater than 200%, and the results are shown in table 1.
4. Appearance: the smoothness of the surface of the high-temperature nylon prepared in the example and the presence of floating fibers were observed, wherein the surface was smooth, the surface was excellent without floating fibers, the surface was slightly uneven, the floating fibers were medium, the surface was rough, and the floating fibers were increased, and the results are shown in table 1.
Table 1 performance characterization test
Examples Wear resistance Fluidity of the resin Appearance of the product
1 Level 1 Level 1 Stage 2
2 Level 1 Level 1 Level 1
3 Level 1 Stage 2 Level 1
4 Stage 2 Level 1 Level 1
5 Stage 2 Stage 2 Level 1
According to the test results, the nylon material provided by the invention has good processing performance, and can obtain nylon products with low friction, low abrasion and high temperature resistance.
It is to be understood that the embodiments described herein are to be considered in a descriptive sense only and not for purposes of limitation. Descriptions of features, advantages, or aspects within various embodiments should be considered as available for other similar features, advantages, or aspects in other embodiments.

Claims (10)

1. The low-friction low-abrasion high-temperature nylon is characterized by comprising the following raw materials in parts by weight: 100 parts of semi-aromatic nylon, 30-60 parts of reinforcing material and 2-10 parts of inorganic filler.
2. The low-friction low-abrasion high-temperature nylon according to claim 1, wherein the semi-aromatic nylon is prepared from aromatic dibasic acid and aliphatic diamine, the aromatic dibasic acid is terephthalic acid and/or isophthalic acid, and the aromatic diamine is selected from one or more of butanediamine, pentanediamine, hexanediamine, heptanediamine and octanediamine.
3. The low friction, low abrasion, high temperature nylon of claim 1 wherein the reinforcement material comprises inorganic reinforcement fibers comprising at least one of glass fibers, carbon fibers, aramid fibers, basalt fibers.
4. The low friction, low abrasion, high temperature nylon of claim 3 wherein the reinforcement material further comprises an organic reinforcement material comprising one or more of polyphenylene sulfide, polyester, polyurethane.
5. The low-friction low-abrasion high-temperature nylon according to claim 4, wherein the inorganic reinforcing fiber is a modified inorganic reinforcing fiber, and the modified reinforcing fiber is prepared from raw materials including an aminosilane coupling agent and the inorganic reinforcing fiber in a weight ratio of (2-5): 100.
6. the low-friction low-abrasion high-temperature nylon according to claim 4, wherein the organic reinforcing material is a modified organic reinforcing material, and the modified organic reinforcing material is prepared from inorganic particles and an organic reinforcing material in a weight ratio of (3-5): 100.
7. the low-friction low-abrasion high-temperature nylon according to claim 6, wherein the inorganic particles are selected from one or more of calcium carbonate, zinc oxide, magnesium oxide and graphite.
8. The low-friction low-abrasion high-temperature nylon according to any one of claims 1 to 7, wherein the inorganic filler is one or more selected from montmorillonite, silicate, carbon black, graphite and diatomite.
9. The low-friction low-abrasion high-temperature nylon according to claim 8, wherein the inorganic filler is a modified inorganic filler, and the modified inorganic filler is prepared from a fluorine-containing silane coupling agent and an inorganic filler in a weight ratio of (1-3): 100.
10. the preparation method of the low-friction low-abrasion high-temperature nylon according to any one of claims 1 to 9, which comprises the following steps: and blending and extruding the preparation raw materials of the high-temperature nylon to obtain the high-temperature nylon.
CN202110777113.2A 2021-07-09 2021-07-09 Low-friction low-abrasion high-temperature nylon and preparation method thereof Pending CN113429783A (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101885914A (en) * 2010-07-13 2010-11-17 东莞市意普万工程塑料有限公司 Composite material special for automobile engine oil pan and preparation method thereof
CN104448809A (en) * 2013-09-25 2015-03-25 上海杰事杰新材料(集团)股份有限公司 Glass fiber/mineral composite enhanced modified semi-aromatic nylon material and preparation method thereof
CN106147221A (en) * 2015-04-28 2016-11-23 株洲时代新材料科技股份有限公司 Fiberglass reinforced fire retardant heat conduction semiaromatic copolymer nylon composite and preparation method thereof
CN106947247A (en) * 2016-01-07 2017-07-14 上海杰事杰新材料(集团)股份有限公司 Composite modified semi-aromatic nylon/polyphenylene oxide composite material of glass fibre-mineral and preparation method thereof
JP2017210513A (en) * 2016-05-24 2017-11-30 旭化成株式会社 Polyamide resin composition and molding
CN107446346A (en) * 2017-09-27 2017-12-08 株洲时代新材料科技股份有限公司 A kind of wear-resisting high-temperature nylon composite of fibre reinforced and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101885914A (en) * 2010-07-13 2010-11-17 东莞市意普万工程塑料有限公司 Composite material special for automobile engine oil pan and preparation method thereof
CN104448809A (en) * 2013-09-25 2015-03-25 上海杰事杰新材料(集团)股份有限公司 Glass fiber/mineral composite enhanced modified semi-aromatic nylon material and preparation method thereof
CN106147221A (en) * 2015-04-28 2016-11-23 株洲时代新材料科技股份有限公司 Fiberglass reinforced fire retardant heat conduction semiaromatic copolymer nylon composite and preparation method thereof
CN106947247A (en) * 2016-01-07 2017-07-14 上海杰事杰新材料(集团)股份有限公司 Composite modified semi-aromatic nylon/polyphenylene oxide composite material of glass fibre-mineral and preparation method thereof
JP2017210513A (en) * 2016-05-24 2017-11-30 旭化成株式会社 Polyamide resin composition and molding
CN107446346A (en) * 2017-09-27 2017-12-08 株洲时代新材料科技股份有限公司 A kind of wear-resisting high-temperature nylon composite of fibre reinforced and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
张凤翻等: "《热固性树脂基复合材料预浸料使用手册》", 30 June 2019 *

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